Self-adjusting coordination of carboxylate for constructing stable 4-con-nected tetrazolate porous frameworks with luminescence

Herein, a series of zinc tetrahedral tetrazolate frameworks (Zn-TTFs) are presented. The reactions of Zn (NO3)2 center dot 6H2O with 5-amino-1H-tetrazole and pyromellitic acid assemble four different Zn-tetrazolate porous networks, namely [Zn2(atz)3(PMA)]center dot guest (1), [Zn2(atz)3.5(PMA)0.25]center dot guest (2), [Zn (atz)1.5(PMA)0.25]center dot guest (3), [Zn3(atz)3(PMA)(Thiourea)(CH3OH)]center dot guest (4), (atz = 5-amino-1H-tetrazole, PMA = pyromellitic acid), whose results demonstrate that rotation of carboxyl group can generate the structural diversity. Interestingly, compound 3 shows a zeolite frl net, while compound 4 exhibits simultaneously super acid and alkali resistance. The luminescent properties based on compound 3 have been studied in the solid state at room temperature, and all of them display lanthanide-based luminescence.